2,4,5-triaminophenols and related compounds

ABSTRACT

New triaminophenol compositions and related compounds are disclosed, as are processes for their preparation and for the preparation of novel salts and diacid complexes from such compounds. Polymers prepared from these compositions can be made into high strength fiber, film, and tape and are useful in applications such as protective apparel, aircraft, automotive components, personal electronics, and sports equipment.

This application claims priority under 35 U.S.C. §119(e) from, andclaims the benefit of, U.S. Provisional Application No. 61/288,422,filed Dec. 21, 2009, which is by this reference incorporated in itsentirety as a part hereof for all purposes.

FIELD OF DISCLOSURE

The disclosure relates to new compositions based on2,4,5-triaminophenols, which can be used in the manufacture ofhigh-performance polybenzimidazole polymers.

BACKGROUND

Aromatic amines and phenols are useful as monomers for high performancepolymers such as aramid polymers and polybenzarenazoles. The structureof the specific monomer used greatly impacts polymer properties such astenacity, solubility, and also the rheological behavior of the polymerduring processing such as spinning. It is thought that replacing highlysymmetric monomers that are currently used (e.g.,2,3,5,6-tetraaminopyridine) with asymmetric monomers would increase thesolubility of the corresponding polymers and the ease with which theyare processed. However, such monomers are often difficult to synthesizeor are unknown. These materials are unknown and have not beensynthesized.

There is a need for asymmetric monomers that can be readily synthesizedand used in the production of high performance polymers such as aramidpolymers and polybenzarenazoles.

SUMMARY

In one embodiment, this invention provides a polymer comprising repeatunits represented by Formula (VI)

wherein R¹, R², and R⁷ are each independently H, alkyl, or aryl; and Qis a C₆ to C₂₀ substituted or unsubstituted monocyclic or polycyclicaromatic nucleus. This invention further provides articles made fromsuch polymer.

In another embodiment, this invention provides a process comprising thesteps:

-   -   (a) preparing a mixture of        -   (i) either a monomer complex represented by the structure of            Formula (V)

-   -    or a mixture of a salt represented by the structure of Formula        (IV)

-   -    and a diacid source selected from the group consisting of        HOOC-Q-COOH, a disodium salt of HOOC-Q-COOH, a dipotassium salt        of HOOC-Q-COOH, or mixtures thereof; wherein R¹, R², and R⁷ are        each independently H, alkyl, or aryl; and Q is a C₆ to C₂₀        substituted or unsubstituted monocyclic or polycyclic aromatic        nucleus;        -   (ii) P₂O₅ and polyphosphoric acid; and        -   (iii) tin metal powder or iron metal powder;    -   (b) stirring the mixture and heating the reactor, under vacuum        with a slight nitrogen purge, at a first temperature of about        100° C. for about one hour; at a second temperature between        about 110° C. and about 140° C. for about 2.5 to about 4.5        hours; at a third temperature between about 130° C. and about        150° C., with the proviso that the third temperature is higher        than the second temperature, for about one hour to about three        hours; and at a fourth temperature between about 150° C., with        the proviso that the fourth temperature is higher than the third        temperature, for about one hour to about four hours.

DESCRIPTION

The following description is exemplary and explanatory only and is notrestrictive of the invention, as defined in the appended claims.

The disclosures herein include new triaminophenols and relatedcompounds, processes for the preparation of such triaminophenols andrelated compounds, processes for the preparation of products into whichsuch triaminophenols and related compounds can be converted, and theproducts obtained and obtainable by such processes.

In the description of the subject matter of this application, thefollowing definitional structure is provided, and, unless indicated tothe contrary, is to be applied to the following terminology as employedherein:

As used herein, the term “free base,” as applied to a triaminophenol, isused to denote a triaminophenol compound per se, for example, Formula(I)

to distinguish it from the acid salt of a triaminophenol or a complex ofthe triaminophenol with a diacid.

As used herein, the term “triaminophenol salt” or “[specifictriaminophenol name or formula reference]salt,” e.g., “Formula (IV)salt” or “TAPH salt” where TAPH means 2,4,5-triamino phenol, denotes acompound formed by reaction of a triaminophenol with “n” equivalents ofan acid (“A”) such as HCl, acetic acid, H₂SO₄, or H₃PO₄. One example ofa triaminophenol salt is TAPH.2HCl (n=2, A=HCl). The salt may also be ahydrate; one such example is TAPH.3HCl.xH₂O.

As used herein, the term “triaminophenol complex” or “[specifictriaminophenol name][diacid source name] complex denotes a compoundformed by reaction of a triaminophenol with a diacid source. Where thecomplex is to be used as a monomer in a polymerization, it can also bereferred to as a “monomer complex.” One example of a triaminophenolcomplex is TAPH.TA, wherein “TAPH” is 2,4,5-triaminophenol and “TA” isterephthalic acid. (n=2, A=HCl).

As used herein the term “diacid source” refers to the diacid HOOC-Q-COOHitself, a disodium salt of HOOC-Q-COOH, a dipotassium salt ofHOOC-Q-COOH, or mixtures thereof, wherein Q is a C₆ to C₂₀ substitutedor unsubstituted monocyclic or polycyclic aromatic nucleus.

As used herein, the term “XYTA” denotes 2-X-5-Y-terephthalic acid, whereX and Y each independently selected from the group consisting of H, OH,SH, SO₃H, methyl, ethyl, F, Cl, and Br. One example is2,5-dihydroxyterephthalic acid (“DHTA”), in which X═Y═OH. The disodiumor dipotassium salt of the XYTA diacid can be represented by the term“M₂XYTA” where M is Na or K.

As used herein, the term “oleum” denotes fuming sulfuric acid, which isan hydrous and is formed by dissolving excess sulfur trioxide (SO₃) intosulfuric acid.

As used herein, the term “weak base” denotes a base whose pKa at 25° C.is between about 6 and about 11. Such a base has a pKa sufficient toreact with the HCl, but not to deprotonate the phenolic proton.

As used herein, the term “net yield” of P denotes the actual, in-handyield, i.e., the theoretical maximum yield minus losses incurred in thecourse of activities such as isolating, handling, drying, and the like.

As used herein, the term “purity” denotes what percentage of an in-hand,isolated sample is actually the specified substance.

As used herein, the term “alkyl” denotes (a) a C₁˜C₁₂, or C₁˜C₈, C₁˜C₆,or C₁˜C₄, straight-chain or branched, saturated or unsaturated,substituted or unsubstituted, hydrocarbyl radical; or (b) a C₃˜C₂, or C₃˜C₆, cyclic aliphatic, saturated or unsaturated, substituted orunsubstituted, hydrocarbyl radical that is either bonded directly to thering or to N or O, or is bonded to the ring or to N or O through a C₁˜C₆straight-chain or branched, saturated or unsaturated, substituted orunsubstituted, hydrocarbyl radical. A C₁˜C₁₂ straight-chain or branched,saturated or unsaturated, substituted or unsubstituted, hydrocarbylradical suitable for use herein may include, for example, a methyl,ethyl, n-propyl, i-propyl, n-butyl, sec-butyl, tert-butyl, n-pentyl,n-hexyl, n-octyl, trimethylpentyl, allyl and propargyl radical. Anunsaturated aliphatic radical may include one or more double bonds, suchas in a dienyl or terpenyl structure, or a triple bond such as in anacetylenyl structure. A C₃˜C₁₂ cyclic aliphatic, saturated orunsaturated, substituted or unsubstituted, hydrocarbyl radical suitablefor use herein may include, for example, an alicyclic functional groupcontaining in its structure, as a skeleton, cyclohexane, cyclooctane,norbornane, norbornene, perhydro-anthracene, adamantane, ortricyclo-[5.2.1.0^(2.6)]-decane groups.

As used herein, the term “aryl” denotes a C₆˜C₁₂, or C₆˜C₁₀, aromaticsubstituted or unsubstituted hydrocarbyl radical that is either bondeddirectly to the ring or to N or O, or is bonded to the ring or to N or Othrough a C₁˜C₆ straight-chain or branched, saturated or unsaturated,substituted or unsubstituted, hydrocarbyl radical. A C₆˜C₁₂ aromaticsubstituted or unsubstituted hydrocarbyl radical suitable for use hereinmay include, for example, a radical derived from a benzyl, phenyl,biphenyl, naphthyl, anthracenyl, xylyl, toluoyl or cunmenyl structure;including, for example, a phenyl, methylphenyl, ethylphenyl,n-propylphenyl, n-butylphenyl, t-butylphenyl, p-chlorophenyl,p-bromophenyl, naphthyl or ethyl naphthyl radical.

As used herein the term “unsubstituted hydrocarbyl radical” contains noatoms other than carbon and hydrogen.

As used herein, the term “substituted hydrocarbyl radical” is defined asa radical in which

-   -   one or more heteroatoms selected from O, N, S and P may        optionally be substituted for any one or more of the in-chain        (i.e. non-terminal) or in-ring carbon atoms, provided that each        heteroatom is separated from the next closest heteroatom by at        least one and preferably two carbon atoms, and that no carbon        atom is bonded to more than one heteroatom; and/or    -   one or more halogen atoms may optionally be bonded to a terminal        carbon atom.        In addition, however, a substituted C₃˜C₁₂ cyclic aliphatic,        saturated or unsaturated hydrocarbyl radical, or a substituted        C₆˜C₁₂ aromatic hydrocarbyl radical, may contain one or more        C₁˜C₈, or C₁˜C₄, straight-chain or branched, saturated or        unsaturated, hydrocarbyl radicals bonded to a carbon atom in the        ring structure, such radical itself optionally being substituted        with one or more heteroatoms selected from O, N, S and P, and/or        containing one or more halogen atoms, subject to the conditions        set forth above.

In various embodiments of this invention, new compounds or compositionsrepresented by the structures of Formulas (I) through (V) below areprovided.

Also provided are novel polymers, or polymer compositions, comprisingrepeat units represented by Formula (VI).

In Formulas (I) through (VI),

R¹ and R² are each independently H, alkyl, or aryl;

R³ and R⁴ are each independently H, alkyl or aryl or may be joined toform an aliphatic ring structure;

R⁵ and R⁶ are each independently H, alkyl or aryl or may be joined toform an aliphatic ring structure;

R⁷ and R⁸ are each independently H, alkyl or aryl or may be joined toform an aliphatic ring structure;

R⁹ is n-propyl, isopropyl, a C₄ to C₈ tertiary alkyl, or a C₇ to C₁₈substituted or unsubstituted benzyl;

n is 1 to 10;

A is an acid, e.g., HCl, acetic acid, H₂ SO₄, or H₃PO₄; and

Q is a C₆ to C₂₀ substituted or unsubstituted monocyclic or polycyclicaromatic nucleus.

In one embodiment of the composition represented by Formula (I), R¹, R²,R³, R⁴, R⁵, R⁶, R⁷, and R⁸ are each H. This compound (Formula (VII)) is2,4,5-triaminophenol (“TAPH”).

In another embodiment of the composition represented by Formula (I), R¹and R² are each independently H, alkyl, or aryl, R³ is H, R⁴ is alkyl orH, and, of the four groups R⁵, R⁶, R⁷, and R⁸, any three are H and thefourth is H, alkyl, or aryl. An example of this embodiment is shownbelow:

In another embodiment, a process is provided for preparing compositionsof Formula (I) wherein each of R³, R⁴, R⁵, and R⁶ is H, represented byFormula (IX)

by

-   -   (a1) monoaminating a composition of Formula (X),

wherein each Z is independently Cl or Br, by heating a suspension of thecomposition of Formula (X) in solvent to a temperature in the range ofabout 60° C. to about 140° C. and contacting it with an aqueous solutionof at least 2.0 equivalents HNR⁷R⁸to produce a composition of Formula(XI)

-   -   (b1) reacting the composition of Formula (XI) with benzyl        alcohol and at least 1.0 equivalent of NaOH or of sodium        benzyloxide to produce a composition of Formula (XII);

-   -   (c1) hydrogenating the composition of Formula (XII) by        contacting the reaction mixture formed in step (b1) with        hydrogen at a pressure in the range of about 0.31 to about 3.45        MPa and a temperature in the range of about 20° C. to about        1.00°: for sufficient time to hydrogenate the composition of        Formula (XII), thereby producing a reaction mixture comprising a        composition of Formula (IX) and toluene;    -   (d1) contacting the reaction mixture formed in step (c1) with an        aqueous solution comprising 1 to 2 equivalents of acid per mol        of 2,4,5-triaminophenol and, optionally, heating the solution,        thereby dissolving the 2,4,5-triaminophenol;    -   (e1) filtering the reaction mixture, thereby removing the spent        hydrogenation catalyst;    -   (f1) extracting the toluene from the reaction mixture; and    -   (g1) adjusting the pH of the extracted, filtered reaction        mixture to a value between about 5 and about 7, by adding a base        wherein said base does not increase the solubility of the        Formula (IX) composition, thereby precipitating the composition        of Formula (IX) from the reaction mixture.

The composition represented by Formula (X) may be prepared by nitrationof the corresponding dihalobenzene according to the method described incopending U.S. patent application Ser. No. 12/335,959, which is herebyincorporated by reference in its entirety for all purposes; by admixinga dihalobenzene represented by the structure of Formula (XIII)

wherein each Z is independently Cl or Br, with nitric acid, sulfuricacid, and oleum or SO₃, to form a reaction mixture that is characterizedby (i) a concentration of nitric acid therein that is in the range ofabout 2.0 to about 2.3 moles per mole of dihalobenzene; (ii) aconcentration of SO₃ therein that is in the range of about 1 to about 3moles per mole of dihalobenzene; (iii) a concentration of dihalobenzenetherein that is in the range of about 12 to about 24 weight percent; and(iv) a temperature of up to about 120° C.; and stirring the reactionmixture at a temperature in the range of about −10° C. to about 70° C.to form a 1-5 dihalodinitrobenzene product represented by the structureof Formula (X). In an embodiment, each Z is Cl and R¹ and R² are each H;i.e., the compound of Formula (X) is 1,3-dichloro-4,6-dinitrobenzene andthe Formula (XIII) dihalobenzene is 1,3-dichlorobenzene, which iscommercially available.

The monoamination of the dihalodinitrobenzene can be carried out asdescribed in U.S. Provisional Application No. 61/288,436, which is bythis reference incorporated in its entirety as a part hereof for allpurposes. In step (a1), a suspension of the composition of Formula (X)in solvent is heated to a temperature in the range of about 60° C. toabout 140° C., preferably about 100° C. to about 135° C., and morepreferably about 130° C., to dissolve the composition of Formula (X) ina solvent. A suitable solvent is an organic solvent inert to thereaction such as an aliphatic dihydric alcohol, such as ethylene glycol(“glycol”). The resulting solution is contacted at that temperature withan aqueous solution of HNR⁷R⁸ for approximately two to four hours closeto ambient pressure; the HNR⁷R⁸ solution is fed as it is consumed, asindicated by any convenient analytical technique (e.g., pH monitoring ormeasuring the flow rate of HNR⁷R⁸ in the gas phase above the reactionmixture). in a preferred embodiment, the compound represented by Formula(XI) is 1-amino-3-chloro-4,6-dinitrobenzene. At least 2.00, preferablyabout 2.03 to about 2.07, equivalents of HNR⁷R⁸ are required. Atreaction completion, the composition of Formula (XI) thereby producedcan be directly isolated from the reaction mixture since it is onlysparingly soluble in suitable solvents such as glycol at temperaturesbelow 50° C.; impurities remain in solution, and net yields of 85% havebeen found at greater than 98% purity for1-amino-3-chloro-4,6-dinitrobenzene specifically.

The composition of Formula (XI) is filtered, typically at about 60° C.,and washed with solvent. in step (b1), the wet cake is then slurriedwith benzyl alcohol. About one to about two equivalents of base (e.g.,NaOH as a slurry in benzyl alcohol, or a solution of the sodium salt ofbenzyl alcohol, Na—O—CH₂-Ph, also known as sodium benzyloxide) areadded. The composition of Formula (XII) thereby produced is mixed withcold (e.g., about 10° C. to about 30° C. methanol/water (e.g., a 50:50mixture of methanol and water by volume), and isolated by filtration,slurried with water, and transferred to a hydrogenation reactor as asuspension.

The composition of Formula (XII) is hydrogenated in step (c). Thehydrogenation reactor contains a hydrogenation catalyst. Examples ofsuitable hydrogenation catalysts include without limitation Pd/C andPt/C and mixtures thereof, optionally containing other metals fromGroups VIII through X such as Fe. The groups are as described in thePeriodic Table in Advanced Inorganic Chemistry by F. A. Cotton and G.Wilkinson, Interscience New York, 2nd Ed. (1966). Of these, Pd/C andPt/C, e.g., 10% Pd/C and 1.0% Pt/C, are preferred. The catalyst istypically used in the amount of about 0.5 to about 5.0 wt % metal basedon 1-benzyloxy-3-amino-4,6-dinitrobenzene.

The hydrogenation reactor is purged with nitrogen and then hydrogen.Deaerated water is then added to the reactor. The aqueous suspension iscontacted with hydrogen to form a reaction mixture. The reaction iscarried out at a temperature in the range of about to 20° C. to 100° C.,preferably about 60° C. to about 85° C., and a hydrogen pressure ofabout 45 to about 500 psi (0.31 to 3.45 MPa) preferably about 300 psi(2.07 MPa). Reaction continues for a time sufficient to consume about6.5 to about 7.5 mol equivalents of hydrogen, thereby producing thecomposition of Formula (IX) and toluene. The toluene can be extractedusing hexanes. The time required for the hydrogenation depends on thedetails of the specific set up but is typically about 2 hours.

The composition of Formula (XII) and the process for making it by steps(a1) and (b1) are a specific example of novel compositions representedby Formula (III)

and a process for making them, wherein R⁹ is n-propyl, isopropyl, a C₄to C₁₈ tertiary alkyl, or a C₇ to C₁₈ substituted or unsubstitutedbenzyl. In general, the composition represented by Formula (II) whereinR⁹ is benzyl, can be made by:

-   -   (b2) monoaminating a composition of Formula (X),

wherein each Z is independently Cl or Br, by heating a suspension of thecomposition of Formula (X) in solvent to a temperature in the range ofabout 60° C. to about 140° C. and contacting it with an aqueous solutionof HNR⁷R⁸ to produce a composition of Formula (XI); and

-   -   (c2) reacting the composition of Formula (XI) with the alcohol        R⁹OH and about 1 to about 2 equivalents of NaOH or of the sodium        salt of R⁹OH, thereby producing a composition represented by        Formula (III)

In the composition represented by Formula (XII), R⁹ is benzyl. Anotherembodiment is represented by Formula (XIV), in which R¹, R², R⁷, and R⁸are each H and R⁹ is benzyl.

Novel compositions represented by Formula (II)

are O-alkylated versions of the compositions represented by Formula (I).In one embodiment, represented by Formula (XV), R¹, R², R³, R⁴, R⁵, R⁶,R⁷, and R⁸ are each —H.

In another embodiment of the composition represented by Formula (II), R¹and R² are each independently H, alkyl, or aryl, R³ is H, R⁴ is alkyl orH, and, of the four groups R⁵, R⁶, R⁷, and R⁸, any three are H and thefourth is H, alkyl, or aryl. An example of this embodiment isrepresented by Formula (XVI), in which R¹ is methyl, R², R³, R⁴, R⁵, R⁶,and R⁷ are each H, and R⁸ is methyl.

To produce compositions represented by Formula (I) or Formula (II)wherein at least one of R³, R⁴, R⁵, and R⁶ is alkyl or aryl, a compoundof Formula (IX) or Formula (XVII),

respectively, could be prepared and then alkylated or arylated, e.g.,using an alky or aryl halide or pseudo halide as known by those skilledin the art. Alternatively, compounds of Formula (I) wherein at least oneof R³, R⁴, R⁵, and R⁶ is alkyl or aryl could be produced by reductiveamination of the compound of Formula (XII) using an aldehyde andhydrogen with the appropriate amine.

In another embodiment, a process is provided for the efficientproduction of novel, high-purity salts represented by Formula (IV)(“Formula (IV) salt”)

wherein n is 1 to 10 and A is an acid, e.g., HCl, acetic acid, H₂SO₄, orH₃PO₄, that can be converted to the free base (i.e., the composition ofFormula (IX) wherein R⁸ is H) or to a novel aromatic diacid complex ofthe free base with a diacid source, represented by Formula (V),

of high enough purity for use in making a high molecular weight polymermaterial for producing high-performance fibers. The salt may also be ahydrate; one such example is 2,4,5-triaminophenol.3HCl.xH₂O(“TAPH.3HCl.xH₂O”). In one embodiment, A is HCl and n is 2 to 4. In oneembodiment, to prepare the Formula (IV) salt, the composition of Formula(IX) is prepared as described above, slurried in water, and contactedwith an acid to form and precipitate the Formula (IV) salt. The mixturecontaining the precipitated Formula (IV) salt is then cooled to about 5°C. to about 15° C., stirred, and filtered. The Formula (IV) salt is thenwashed. It may be washed with deaerated aqueous acid, such as HCl (33%)and then optionally with deaerated ethanol or methanol to produce a wetcake material.

Whether aqueous acid or cold water is used as a wash, it may be possibleto eliminate the ethanol or methanol wash and dry directly from aqueouswet cake or simply use the wet cake in subsequent processing. It islikely that in a commercial process one would only wash with HCl_(aq)and, if desired, dry directly.

The resulting wet cake material (Formula (IV) salt) can be used insubsequent processing without drying or can be dried, for example at apressure less than 400 Torr and a temperature of about 30° C. to about50° C., under a stream of N₂. The dried product is preferably kept undernitrogen.

In another embodiment, a process is provided for preparing novelcomplexes of Formula (V),

wherein Q is a C₆ to C₂₀ substituted or unsubstituted monocyclic orpolycyclic aromatic nucleus.

Examples of Q include without limitation:

One or more heteroatoms (such as N, O, S) may be present in the ring(s)of Q, for example, as shown below:

In one embodiment, Q is represented by the structure of Formula (XVIII)

wherein X and Y are each independently selected from the groupconsisting of H, OH, SH, SO₃H, methyl, ethyl, F, Cl, and Br. Preferably,X═Y═OH (i.e., the diacid is 2,5-dihydroxyterephthalic acid) or X═Y═H(i.e., the diacid is terephthalic acid). When X═Y═H, the diacid isreferred to as “XYTA”.

In one embodiment (“Option A”), the Formula (IV) salt is precipitatedand washed as described above, then slurried with water. Base (e.g.,NaHCO₃), sufficient to neutralize the reaction mixture, and a diacidsource are then added to the slurry to form and precipitate the complex,Formula (V). As used herein the term “diacid source” refers to thediacid HOOC-Q-COOH itself, the salt a disodium salt of HOOC-Q-COOH, adipotassium salt of HOOC-Q-COOH, or mixtures thereof.

Alternatively (“Option B”), after the reaction mixture produced inhydrogenation step (c1) has been filtered and the toluene removed byextraction, typically using hexanes, the reaction mixture containing thecomposition of Formula (IX) (with R⁸═H) can be combined directly withthe base and the diacid source to form and precipitate the complex ofFormula (V). In another alternative (“Option C”), filtered free base(Formula (IX) with R⁸═H) can be dissolved in about 1-2 equivalents ofacid (e.g., HCl) and the solution so produced contacted with the baseand the diacid source to form the complex of Formula (V).

In the complex described by Formula (V), it is important that the ratioof the free base (Formula (IX) with R⁸═H) to the diacid source be 1:1.This allows the production of high molecular weight polymer from thecomplex and high strength fiber from the polymer. In some instances,including but not limited to, complexes wherein the free base is2,4,5-triaminophenol (“TAPH”), i.e., the desired complex is representedby Formula (XIX),

the use of a strong base such as aqueous sodium hydroxide or aqueouspotassium hydroxide in the Option A, B, or C process can cause the freebase to diacid ratio in the complexes so produced to deviate from 1:1.In such cases, a preferred process is to dissolve the Formula (IV) salt,e.g., TAPH.2HCl, in water and contact that solution with the diacidsource in an aqueous solution of a weak base such as NaHCO₃. As usedherein, the term “weak base” denotes a base whose pKa at 25° C. isbetween about 6 and about 11. Such a base has a pKa sufficient to reactwith the HCl, but not to deprotonate the phenolic proton. This processcan be performed under mild conditions, e.g., from ambient temperaturesto about 50° C. The ratio of equivalents of the Formula (IV) salt toequivalents of diacid source is from 1.0:1.0 to 1.5:1.0, preferably1.025:1.00 to 1.10 to 1.00 equivalents.

Various designs are possible for combining the Formula (IV) salt withthe diacid source and aqueous base to produce the complex. For example,the base and the diacid source are most conveniently added as a singlesolution. In other embodiments, the Formula (V) salt in an acid solutioncould be introduced into a vessel containing a basic diacid sourcesolution, or the diacid source stream could be fed into the vesselcontaining the Formula (V) salt in an acid solution. Which design isbest for a specific situation will be evident to one of skill in theart.

The Formula (V) complex is recovered from the reaction mixture byfiltration at a temperature in of the range of about 5° C. to about 50°C., preferably about 10° C. to about 15° C., and washed with water andmethanol, typically at a temperature in the range of about 15° C. toabout 40° C., and then dried. The washed and dried Formula (V)-complexis kept under nitrogen to protect it from oxygen. It is of high enoughquality and purity to produce polybenzimidazole polymer of high enoughmolecular weight to make high performance fibers.

The Option A embodiment discussed above can produce higher purityFormula (V) complex than Options B or C. On the other hand, Options 13and C have fewer steps, generate less waste and also require less acid(e.g., HCl) and base (e.g., NaHCO₃), thus lessening raw material andhandling costs. All disclosed embodiments produce polymer grade materialsuitable for the manufacture of high-performance fibers.

Oxygen is excluded throughout all steps of the processes of making thefree base, the Formula (IV) salt, and the Formula (V) complex. Deaeratedwater and deaerated acid are used. A small amount of a reducing agent(e.g., about 0.5% tin powder) is optionally added to one or more ofaqueous suspensions or aqueous solutions containing the triaminophenolfree base, the Formula (IV) salt, or the Formula (V) complex during theprocess to reduce impurities caused by oxidation and to prevent furtherimpurity formation by that route.

In another embodiment, novel polymer compositions are providedcomprising a composition of Formula (I) or Formula (III) as a monomer.Articles comprising these polymers are also provided. Examples of sucharticles include without limitation fiber, film, and tape. In oneembodiment, novel polymer compositions are provided comprising repeatunits represented by Formula (VI).

wherein R¹, R², and R⁷ are each independently H, alkyl, or aryl; and Qis a C₆ to C₂₀ substituted or unsubstituted monocyclic or polycyclicaromatic nucleus as defined above.

Polymers comprising repeat units represented by Formula (VI) can beprepared at high molecular weight from a mixture of a triaminophenolsalt represented by Formula (IV) (e.g., TAPH.2HCl) with HOOC-Q-COOH inpolyphosphoric acid, or from a complex represented by Formula (V) attemperatures from about 100° C. to about 180° C.

In one embodiment, represented by Formula (XX), R¹, R², and R⁷ are eachH and Q is 1,4-phenylene.

The polymer represented by Formula (XX) can be made by polymerizing the1:1 monomer complex of 2,4,5-triaminophenol with terephthalic acid(“TAPH.T complex”); or by polymerizing a mixture of a TAPH salt (e.g.,TAPH.2HCl) and terephthalic acid.

In another embodiment, represented by Formula (XXI), R¹, R², and R⁷ areeach H and Q is 2,5-dihydroxy-1,4-phenylene (C₆H₄).

The polymer represented by Formula (XX) can be made by polymerizing the1:1 monomer complex of 2,4,5-triaminophenol with2,5-dihydroxyterephthalic acid (“TAPH.DHTA complex”); or by polymerizinga mixture of a TAPH salt (e.g., TAPH.2HCl) and 2,5-dihydroxyterephthalicacid.

The polymerization of the monomer complex is typically carried out in areactor suitably equipped with connections for purging with inert gas,applying a vacuum, heating and stirring. Monomer complex, P₂O₅,polyphosphoric acid (“PPA”) and powdered metal (for example, tin or ironmetal) are typically added to the reactor. The reactor is typicallypurged, heated and mixed to effect polymerization. In a preferredembodiment, about 20 parts by weight of monomer complex, about 10 partsof P₂O₅, 100 parts of PPA, and about 0.1 parts tin or iron metal areadded to a suitable reactor. The contents of the reactor are stirred atabout 60 rpm and heated to about 100° C. for about one hour under vacuumwith a slight nitrogen purge. The temperature is typically raised to atleast 110° C., preferably at least about 120° C., and preferably notmore than 140° C. for a few more hours, preferably about four hours. Thetemperature is then raised and held at a higher temperature, at leastabout 130° C., more typically at least about 140° C., and preferably atabout 150° C. for about an hour, more preferably about three hours. Thetemperature is subsequently then raised and held at a highertemperature, at least about 150° C., more typically at least about 170°C., and preferably at about 180° C. for about an hour, more preferablyabout three hours. The reactor is typically flushed with nitrogen and asample of the polymer solution is taken for viscosity determination.

Typically, the polymers so produced from monomer complexes formpolybenzarenazoles that are characterized as providing a polymersolution having an inherent viscosity of at least about 29 dl/g at 30°C. at a polymer concentration of 0.05 g/dl in methanesulfonic acid. Incertain embodiments, the metal powder is present in an amount of about0.1 to about 0.5 weight percent based on monomer complex.

In certain embodiments, the reaction mixture includes polyphosphoricacid having an equivalent P₂O₅ content of at least about 81 percentafter polymerization, and more preferably at least about 86 percentafter polymerization. in certain embodiments, the reaction mixtureincludes polyphosphoric acid having an equivalent P₂O₅ content of atleast about 81 percent after contacting, in polyphosphoric acid, themonomer complex with metal powder, the metal powder added in an amountof from about 0.05 to about 0.9 weight percent, based on the totalmonomer weight and polymerizing the monomers in polyphosphoric acid toform the polymer solution. In certain of these embodiments, the ratio ofequivalents of the triaminophenol to the diacid source is typically atleast about 1 to 1, more typically at least about 1.05 to 1, even moretypically at least about 1.075 to 1, and further typically at leastabout 1.15 to 1.

A solution of such polymers at about 10 to about 30 wt % inpolyphosphoric acid can be used to prepare high strength fiber, films,and tapes, which can be used, for example, as reinforcement materialsfor thermoplastic and thermoset matrices. Fibers may also be cut andused as staple fiber or, when fibrillated, as pulp. Useful articlescomprising the polybenzarenazole polymers described herein includewithout limitation: protective apparel (e.g., body armor, industrialgloves, flame retardant apparel); aircraft applications (e.g.,components of aircraft cabin, flooring and interiors, landing geardoors; rotor blades; space craft; maritime vessels; automotivecomponents (e.g., tires, friction and sealing applications, brake pads,belts, gaskets, hoses, composites, vehicular armor); sports equipment;and personal electronics.

The materials, methods, and examples herein are illustrative only and,except as specifically stated, are not intended to be limiting.

EXAMPLES

The present invention is further defined in the following examples. Itshould be understood that these examples, while indicating preferredembodiments of the invention, are given by way of illustration only.From the above discussion and these examples, one skilled in the art canascertain the essential characteristics of this invention, and withoutdeparting from the spirit and scope thereof, can make various changesand modifications of the invention to adapt it to various uses andconditions.

All water used was deaerated and de-ionized water. The examples werecarried out under exclusion of oxygen.

The meaning of abbreviations is as follows: “ACDNB” means1-chloro-3-amino-4,6-dinitrobenzene, “BOB” means1-benzyloxy-3-amino-4,6-dinitrobenzene, “cm” means centimeter(s), “d”means density, “DADNB” means 1,3-diamino-4,6-dinitrobenzene, “DCDNB”means 1,3-dichloro-4,6-dinitrobenzene, “dl” means deciliter(s), “equiv”means equivalent(s), “g” means gram(s), “gal” means gallon, “GC” meansgas chromatography, “¹H-NMR” means proton nuclear magnetic resonancespectroscopy, “h” means hour(s), “L” means liter(s), “mL” meansmilliliter(s), “L” means milliliter(s), “min” means minutes, “mol” meansmole(s), “MPa” means megapascals, “PPA” means polyphosphoric acid, “psi”means pounds per square inch, “rpm” means revolutions per minute, and“η_(inh)” means inherent viscosity.

Example 1 Preparation of DCDNB

To a 1 L 3-neck round bottom flask equipped with external ice cooling,mechanical stirrer, addition funnel, N₂ inlet, and thermometer was added126 g (2 mol) fuming nitric acid (d=1.54 g/cm³), followed by 208 gsulfuric acid and 508 g 30% oleum (2.2 molar equiv SO₃), maintaining atemperature between 10 and 40° C. Subsequently, 140 g (0.95 mmol)1,3-dichlorobenzene (Toray Ltd., Tokyo, Japan, >99% purity) were addedover a time period of 90 min while maintaining a temperature of about 5°C. The ice bath was removed, and the reaction mixture was allowed towarm up to room temperature. It was then heated from room temperature to100° C. over a time period of 45 min. At that point, a small sample ofcrude product was taken from the reaction vessel and poured into icewater. The crude product was extracted with methylene chloride. Analysisby GC and ¹H-NMR indicated a reaction selectivity for1,3-dichloro-4,6-dinitrobenzene of 92%. After 15 rain at 100° C., thereaction mixture was allowed to cool to room temperature over 2 h andthen cooled to 5° C. over 30 min, after which it was filtered through aglass fritted funnel and washed with 300 mL water followed by 200 mL 10%aqueous NH₃ solution. Analysis indicated a net content of about 184 gof >98% pure product (˜80% net yield) and the dry mass content of thewet cake was about 90%.

Example 2 Preparation of ACDNB from DCDNB

A three-necked flask was equipped with a thermocouple, magnetic stirrer,septa through which a tube was added for the addition of the ammoniumhydroxide solution and reflux condenser with gas outlet. The DCDNB andethylene glycol were added to the flask. The ammonium hydroxide waspumped into the vessel at a rate of 0.607 mL/min at a temperature of138° C. A total of 6.7 moles of ammonium hydroxide were added.Conversion to product was controlled by GC analysis. The reactionsuspension was allowed to cool to 60° C. before it was filtered and theyellow-to-bronze colored fine crystalline product was washed with twoportions of about 50 mL of 60° C. ethylene glycol followed by 2×50 mLwater. GC analysis showed that the reaction solution contained less than1% 1,3-dichloro-2,4-dinitrobenzene and no more than 3%1,3-diamino-2,4-dinitrobenzene. The net yield was about 75% and thepurity was >97%.

Example 3 Preparation of 1-benzyloxy-3-amino-4,6-dinitrobenzene (“BOB”)from ACDNB

A three-necked 2 L flask was equipped with a thermocouple, magneticstirrer and reflux condenser with gas outlet. The gas outlet wasequipped with a three-way-splitter connecting the outlet to an oilbubbler and an N₂ line. The ACDNB and benzyl alcohol were added to theflask and heated to 50° C. while under a N₂ blanket. The solid sodiumhydroxide was added to the reaction as a ground powder in 10 equalportions over 3 h such that the reaction temperature did not exceed 55°C. During the course of the reaction, a deep-red color was producedalong with a slight exotherm of a few degrees. Conversion to product wascontrolled by LC analysis. After addition of 1.05 equivalent of base thereaction was allowed to return to room temperature. The reactionsuspension was poured into a 50:50 wt % solution of cold methanol andwater. This mixture was stirred and then filtered. The solid product oflight bronze color was further rinsed with another portion of 50:50methanol and water. After a final rinse with cold methanol, the filtercake was air-dried. The net yield was about 80% and the purity was 96%.

Example 4 Preparation of TAPH.2HCl from BOB

A 1-gal (3.79 L) stirred Hastelloy autoclave was charged with 125 g ofBOB prepared in Example 3 and 3.6 g of 10% Pt/C (dry basis, 50% water).The autoclave was purged 10 times with N₂ and 5 times with H₂ at 90 psi(0.62 MPa). Subsequently, 300 mL of deaerated water (purged with N₂overnight) were added and the mixture was pressurized at 60° C. to 300psi (2.07 MPa). Hydrogenation was continued for a total time of about 80min with an approximate uptake of 2.7 moles of H₂ (6.5 equiv). Theexcess hydrogen was released and the autoclave was cooled to 40° C. andpurged twice with N₂, after which 80 g of deaerated HCl_(aq) (36.3%, bytitration) and 175 g of water were added. The mixture was stirred for 1hour, then passed through a metal CUNO filter to remove catalyst. Theautoclave was rinsed with 30 mL of deaerated water. The solution wasdirectly charged into a purged 2 L vessel.

The reaction mixture was extracted with 2×200 mL portions of hexanes,and the organic phase was discarded. The aqueous phase was filteredthrough a filter packed with celite followed by carbon black and sand.About 0.1 g of Sn powder was added to the filtrate. The mixture wasneutralized to pH 6 with aqueous sodium hydroxide (50% wt) and the freebase, TAPH, was isolated by filtration. The free base was subsequentlycombined with water to form a 50% wt slurry. In a separate flask, 300 g(10 equivalents) of concentrated aqueous HCl (approximately 36% wt) wascooled to about 5° C. The free base TAPH slurry was added slowly to thestirred cold HCl solution while maintaining a solution temperature ofabout 5° C. After stirring for an additional 2 h at 5° C., the TAPHhydrochloride salt was isolated by filtration and washed twice withabout 50 mL methanol. The net yield of TAPH hydrochloride salt isolatedwas about 60% and the purity was >99%. Elemental analysis: C, 33.56%; N,19.23%; H, 5.07%; Cl, 33.28%. An X-ray structural determinationconfirmed that the product was TAPH.2HCl.

Example 5 Preparation of TAPH.2HCl from BOB

A 1 L stirred Hastelloy autoclave was charged with 120 g (0.415 moles)of 1-benzyloxy-3-amino-4,6-dinitrobenzene (“BOB”), and 3.6 g of 10%Pd/C. The autoclave was purged 10 times with N₂ and 5 times with H₂ at90 psi (0.62 MPa). Subsequently, 290 g of deaerated water (purged withN₂ overnight) was added and the mixture was pressurized at 60° C. to 300psi (2.07 MPa). Hydrogenation was continued for a total time of about2.5 h. The excess hydrogen was released and the autoclave was cooled to40° C. and purged twice with N₂, after which 80 g of HCl_(aq) in 145 gdeaerated water was added. The mixture was stirred for one hour, andthen passed through a carbon bed filter at about 40° C. to removecatalyst. The filter was rinsed with 30 mL of water. The TAPH.2HClsolution was directly charged into a holdup vessel under N₂ containing 5g of Sn powder.

Example 6 Preparation of TAPH.DHTA from TAPH.2-HCl Solution

6.06 g of K₂DHTA (22.08 mmol) along with 2.69 g of sodium bicarbonate(32.02 mmol) was added to a reaction vessel. This was followed by theaddition of 75 g of deaerated water and heating to 75° C. About 33.75 gof 0.18M TAPH.2HCl salt solution (24.3 mmol) made as described inExample 5 was added to another reaction vessel. The hot solution ofK₂DHTA was subsequently added dropwise into the TAPH.2HCl salt solutionat room temp., with fast stirring, over a period of 10 minutes, whichresulted in precipitation of a light brown solid. This mixture was thencooled to room temp., with stirring, for 1.5 hours. The mixture wassubsequently filtered and washed with ethanol (50 mL). The solid beigeproduct was allowed to dry for 18 hours under vacuum. ¹H-NMR analysisrevealed the TAPH-DHTA ratio as being (1.00:1.01).

Example 7 Preparation of TAPH.T from TAPH.2HCl Solution

3.03 g of terephthalic acid (19.872 mmol) along with 2.05 g of sodiumbicarbonate (40.738 mmol) was added to a reaction vessel. This wasfollowed by the addition of 54 g of deaerated water and heating to 75°C. About 30.375 g of 0.18 M TAPH.2HCl salt solution (21.87 mmol) made asdescribed in Example 5 was added to another reaction vessel along with2.25 g of sodium bicarbonate (26.83 mmol). The hot solution ofterephthalic acid was subsequently added dropwise into the TAPH.2HClsalt solution at room temp., with fast stirring, over a period of 10minutes, which resulted in precipitation of a purple solid. This mixturewas then cooled to room temp., with stirring, for 1.5 hours. The mixturewas subsequently filtered and washed with ethanol (50 mL). The solidpink product was allowed to dry for 18 hours under vacuum. ¹H-NMRanalysis revealed the TAPH-T ratio as being (1.00:1.01).

Example 8 Polymerization of TAPH.T Complex in Polyphosphoric Acid

Into a clean dry 200 mL glass tubular reactor having an inside diameterof 4.8 cm, equipped with the necessary connections for purging nitrogenand applying a vacuum, and around which a heating jacket was arrangedand which further contained double helix shaped basket stirrer, wascharged 14.7 g of monomer complex, 10.92 g of P₂O₅, 54.42 g of PPA witha % P₂O₅; equivalent to 85.5%, and 0.07 g Fe powder. The stirrer wasturned on at 100 rpm and the contents were heated to 100° C. for onehour under vacuum. The temperature was raised and held at 120° C. for 18hours. The temperature was raised and held at 150° C. for 4 hours. Thetemperature was raised and held at 180° C. for 4. hours. The reactor wasflushed with nitrogen gas (“N₂”) and a sample of the polymer solutionwas diluted with methane sulfonic acid to 0.05% concentration. Theη_(inh)=6.6 dl/g.

Example 9 Polymerization of TAPH.DHTA Complex in Polyphosphoric Acid(Glass Tubular Reactor)

into a clean dry 200 mL glass tubular reactor having an inside diameterof 4.8 cm, equipped with the necessary connections for purging nitrogenand applying a vacuum, and around which a heating jacket was arrangedand which further contained double helix shaped basket stirrer, wascharged 10.17 g of TAPH.DHTA complex, 5.81 g of P₂O₅, 64.1 g of PPA witha % P₂O₅ equivalent to 85.4%, and 0.05 g Fe powder. The stirrer wasturned on at 100 rpm and the contents were heated to 100° C. for onehour under vacuum. The temperature was raised and held at 120° C. for 18hours. The temperature was raised and held at 150° C. for 3 hours. Thetemperature was raised and held at 180° C. for 3 hours. The reactor wasflushed with nitrogen gas (“N₂”) and a sample of the polymer solutionwas diluted with methane sulfonic acid to 0.05% concentration. Then_(inh) was 29.3 dl/g.

Example 10 Polymerization of TAPH.DHTA Complex in Polyphosphoric Acid(Twin Cone Reactor)

The following were combined in a clean dry 2CV Model DIT Mixer(available from Design Integrated Technology, Inc, Warrenton, Va.).

-   -   a) 71.62 grams of Polyphosphoric Acid (PPA) with a concentration        of 85.4% P₂O₅,    -   b) 10.57 grams of P₂O₅,    -   c) 0.07 grams of Fe powder (325 mesh and available from VWR        scientific; this amount is 0.4% based on weight of TAPH.DHTA        complex), and    -   d) 17.8 grams of TAPH.DHTA complex (one to one complex of        2,4,5-triaminophenol (TAPH) and 2,5-dihydroxyterephthalic acid        (DHTA)).

The CV Model was a jacketed twin cone reactor that was heated by thecirculation of hot oil through the jacket. This reactor usedintersecting dual helical-conical blades that intermesh throughout theconical envelope of the bowl. The mixer blades were started and set atabout 80 rpm. The reactor was swept with dry N₂ gas followed by avacuum. The temperature of the reaction mixture was measured throughoutusing a thermocouple. The temperature of the reaction mixture was raisedto 100° C. and under vacuum held for 1 hour. The temperature of thereaction mixture was raised to 120° C. and held for 18 hours. Next, thetemperature of the reaction mixture was raised to 150° C. and held for 3hours. Next, the temperature of the reaction mixture was raised to 180°C. and held for 3 hours. The mixer was purged with nitrogen and thepolymer solution was discharged into a glass vessel. The polymer wasremoved from the mixer in the form of a solution in PPA. A sample of thepolymer was separated from the solution and then diluted with methanesulfonic acid (“MSA”) to a concentration of 0.05% polymer solids. Theinherent viscosity of the polymer sample was 29.92 dl/g.

It is to be appreciated that certain features of the invention whichare, for clarity, described above and below in the context of separateembodiments, may also be provided in combination in a single embodiment.Conversely, various features of the invention that are, for brevity,described in the context of a single embodiment, may also be providedseparately or in any subcombination. Further, reference to values statedin ranges include each and every value within that range.

All publications, patent applications, patents, and other referencesmentioned herein are incorporated by reference in their entirety. Unlessotherwise defined, all technical and scientific terms used herein havethe same meaning as commonly understood by one of ordinary skill in theart to which this invention belongs. In case of conflict, the presentspecification, including definitions, will control.

Although methods and materials similar or equivalent to those describedherein can be used in the practice or testing of the present invention,suitable methods and materials are described herein. Unless statedotherwise, all percentages, parts, ratios, etc., are by weight.

When an amount, concentration, or other value or parameter is given aseither a range, preferred range or a list of upper preferable values andlower preferable values, this is to be understood as specificallydisclosing all ranges formed from any pair of any upper range limit orpreferred value and any lower range limit or preferred value, regardlessof whether ranges are separately disclosed. Where a range of numericalvalues is recited herein, unless otherwise stated, the range is intendedto include the endpoints thereof, and all integers and fractions withinthe range. It is not intended that the scope of the invention be limitedto the specific values recited when defining a range.

When the term “about” is used in describing a value or an end-point of arange, the disclosure should be understood to include the specific valueor end-point referred to. As used herein, the terms “comprises,”“comprising,” “includes,” “including,” “containing,” “characterized by,”“has,” “having” or any other variation thereof, are intended to cover anon-exclusive inclusion. For example, a process, method, article, orapparatus that comprises a list of elements is not necessarily limitedto only those elements but may include other elements not expresslylisted or inherent to such process, method, article, or apparatus.Further, unless expressly stated to the contrary, “or” refers to aninclusive or and not to an exclusive or. For example, a condition A or Bis satisfied by any one of the following: A is true (or present) and Bis false (or not present), A is false (or not present) and B is true (orpresent), and both A and B are true (or present).

Use of “a” or “an” are employed to describe elements and components ofthe invention. This is done merely for convenience and to give a generalsense of the invention. This description should be read to include oneor at least one and the singular also includes the plural unless it isobvious that it is meant otherwise.

1. A polymer comprising repeat units represented by Formula (VI)

wherein: R¹, R², and R⁷ are each independently H, alkyl, or aryl; and Qis a C₆ to C₂₀ substituted or unsubstituted monocyclic or polycyclicaromatic nucleus.
 2. The polymer of claim 1 wherein R¹, R², and R⁷ areeach H.
 3. The polymer of claim 1 wherein Q is selected from the groupconsisting of:


4. The polymer of claim 1 wherein Q is represented by the structure ofFormula (XVIII)

wherein X and Y are each independently selected from the groupconsisting of H, OH, SH, SO₃H, methyl, ethyl, F, Cl, and Br.
 5. Thepolymer of claim 4 wherein X═Y═H or X═Y═OH.
 6. The polymer of claim 5wherein R¹, R², and R⁷ are each H.
 7. A process comprising the steps:(a) preparing a mixture of (iv) either a monomer complex represented bythe structure of Formula (V)

 or a mixture of a salt represented by the structure of Formula (IV)

 and a diacid source selected from the group consisting of HOOC-Q-COOH,a disodium salt of HOOC-Q-COOH, a dipotassium salt of HOOC-Q-COOH, ormixtures thereof; wherein R¹, R², and R⁷ are each independently H,alkyl, or aryl; and Q is a C₆ to C₂₀ substituted or unsubstitutedmonocyclic or polycyclic aromatic nucleus; (v) P₂O₅ and polyphosphoricacid; and (vi) tin metal powder or iron metal powder; (b) stirring themixture and heating the reactor, under vacuum with a slight nitrogenpurge, at a first temperature of about 100° C. for about one hour; at asecond temperature between about 110° C. and about 140° C. for about 2.5to about 4.5 hours; at a third temperature between about 130° C. andabout 150° C., with the proviso that the third temperature is higherthan the second temperature, for about one hour to about three hours;and at a fourth temperature between about 150° C., with the proviso thatthe fourth temperature is higher than the third temperature, for aboutone hour to about four hours.
 8. The process of claim 7 wherein themixture contains about 20 parts by weight of monomer complex, about 10parts of P₂O₅, about 100 parts of polyphosphoric acid.
 9. The process ofclaim 7 wherein the tin metal powder or iron metal powder is present inan amount of about 0.1 to about 0.5 weight percent based on monomercomplex.
 10. The process of claim 7 wherein the reaction mixturecomprises polyphosphoric acid having an equivalent P₂O₅ content of atleast about 81 percent after polymerization.
 11. The process of claim 7wherein the ratio of equivalents of the triaminophenol to the diacid isfrom about 1:1 to about 1.15:1.
 12. The process of claim 7 wherein R¹,R², and R⁷ are each H, and Q is either 1,4-phenylene or2,5-dihydtoxy-1,4-phenylene.
 13. An article comprising the polymer ofclaim
 1. 14. The article of claim 13 wherein said article is in the formof fiber, film, or tape.
 15. The article of claim 13 wherein saidarticle is a member of the group consisting of: protective apparel;components of aircraft cabins, flooring and interiors, landing geardoors; rotor blades; space craft; maritime vessels; automotivecomponents; sports equipment; and personal electronics.
 16. The articleof claim 15 wherein said article is an automotive component selectedfrom the group consisting of tires, friction and sealing applications,brake pads, belts, gaskets, hoses, composites, and vehicular armor.